CN114854416B - Near-infrared silver-gold-selenium fluorescent quantum dot and preparation method and application thereof - Google Patents
Near-infrared silver-gold-selenium fluorescent quantum dot and preparation method and application thereof Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 91
- IANXFCFDMBNAHB-UHFFFAOYSA-N gold selanylidenesilver Chemical compound [Au].[Ag]=[Se] IANXFCFDMBNAHB-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- KDSXXMBJKHQCAA-UHFFFAOYSA-N disilver;selenium(2-) Chemical compound [Se-2].[Ag+].[Ag+] KDSXXMBJKHQCAA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 22
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010931 gold Substances 0.000 claims abstract description 19
- 229910052737 gold Inorganic materials 0.000 claims abstract description 19
- 239000002798 polar solvent Substances 0.000 claims abstract description 17
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 17
- 239000011669 selenium Substances 0.000 claims abstract description 17
- 238000004729 solvothermal method Methods 0.000 claims abstract description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 239000004332 silver Substances 0.000 claims abstract description 11
- 238000005341 cation exchange Methods 0.000 claims abstract description 9
- 229940091258 selenium supplement Drugs 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000006862 quantum yield reaction Methods 0.000 claims description 7
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 5
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- PMYDPQQPEAYXKD-UHFFFAOYSA-N 3-hydroxy-n-naphthalen-2-ylnaphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(NC(=O)C3=CC4=CC=CC=C4C=C3O)=CC=C21 PMYDPQQPEAYXKD-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 3
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- YWWZCHLUQSHMCL-UHFFFAOYSA-N diphenyl diselenide Chemical compound C=1C=CC=CC=1[Se][Se]C1=CC=CC=C1 YWWZCHLUQSHMCL-UHFFFAOYSA-N 0.000 claims description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910001922 gold oxide Inorganic materials 0.000 claims description 3
- ZVUZTTDXWACDHD-UHFFFAOYSA-N gold(3+);trinitrate Chemical compound [Au+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZVUZTTDXWACDHD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims description 3
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 claims description 3
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 3
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 3
- 229940045105 silver iodide Drugs 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical compound [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 claims description 3
- NSVHDIYWJVLAGH-UHFFFAOYSA-M silver;n,n-diethylcarbamodithioate Chemical compound [Ag+].CCN(CC)C([S-])=S NSVHDIYWJVLAGH-UHFFFAOYSA-M 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229960001881 sodium selenate Drugs 0.000 claims description 3
- 235000018716 sodium selenate Nutrition 0.000 claims description 3
- 239000011655 sodium selenate Substances 0.000 claims description 3
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052946 acanthite Inorganic materials 0.000 claims description 2
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 229940056910 silver sulfide Drugs 0.000 claims description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 claims description 2
- 229960001471 sodium selenite Drugs 0.000 claims description 2
- 235000015921 sodium selenite Nutrition 0.000 claims description 2
- 239000011781 sodium selenite Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 238000012984 biological imaging Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 8
- 239000012467 final product Substances 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 231100000331 toxic Toxicity 0.000 description 6
- 230000002588 toxic effect Effects 0.000 description 6
- 238000000799 fluorescence microscopy Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- KRRRBSZQCHDZMP-UHFFFAOYSA-N selanylidenesilver Chemical class [Ag]=[Se] KRRRBSZQCHDZMP-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000012632 fluorescent imaging Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000011503 in vivo imaging Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VCEXCCILEWFFBG-UHFFFAOYSA-N mercury telluride Chemical compound [Hg]=[Te] VCEXCCILEWFFBG-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- GGYFMLJDMAMTAB-UHFFFAOYSA-N selanylidenelead Chemical compound [Pb]=[Se] GGYFMLJDMAMTAB-UHFFFAOYSA-N 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
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Images
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention discloses a near infrared silver gold selenium fluorescent quantum dot and a preparation method and application thereof. The preparation method comprises the following steps: carrying out solvothermal reaction on a first uniform mixed reaction system containing a silver source, a selenium source and a weak polar solvent to obtain a silver selenide quantum dot precursor; and (3) carrying out cation exchange reaction on a second uniform mixed reaction system containing a silver selenide quantum dot precursor and a gold source at 0-200 ℃ for 10-72 h to obtain the near infrared silver-gold-selenium fluorescent quantum dot, wherein the fluorescence emission peak wavelength is 800-1350 nm. The silver gold selenium quantum dot is obtained through a simple high-temperature solvothermal method, and then through a cation exchange method, the synthesis process is simple and controllable, the yield is high, the large-scale preparation can be realized, meanwhile, the obtained product is uniform in size, fluorescence emission is in near infrared, the quantum dot has high quantum efficiency and excellent light stability, and the silver gold selenium quantum dot has wide application prospects in the fields of biological imaging, near infrared devices and the like.
Description
Technical Field
The invention relates to a near infrared fluorescent quantum dot and a preparation method thereof, in particular to a near infrared silver gold selenium fluorescent quantum dot with high quantum efficiency and a preparation method and application thereof, belonging to the field of material science.
Background
The fluorescent imaging technology has the advantages of non-contact, visual image, real-time, high sensitivity, economy, convenience, no radiation hazard and the like, and has wide application prospect in biomedical research and clinical practice, in particular in the aspect of fluorescent image surgical navigation. Depending on the wavelength range of the fluorescence imaging, it mainly includes visible light fluorescence imaging (400-650 nm) and near infrared fluorescence imaging (650-1700 nm). In biological imaging, near infrared light can be divided into two optical windows: near infrared I region (650-900 nm, NIR-I) and near infrared (900-1700 nm, NIR-II). NIR-fluorescence is a new fluorescence window discovered in vivo fluorescence imaging studies in the last decade, where the attenuation coefficient of NIR-II photons in living tissue is significantly reduced compared to the visible and NIR-I regions (j.am. Chem. Soc.2020, 142, 14789-14804.) and thus the NIR-II fluorescence has a higher tissue penetration depth and spatial resolution in living imaging.
Quantum dots as an excellent NIR-II fluorescent probe have the following characteristics in vivo imaging studies: high biocompatibility, high quantum efficiency, adjustable excitation and emission wavelength, easy functionalization of the surface, and the like. However, the existing infrared fluorescent quantum dots, such as lead sulfide, cadmium telluride, lead selenide, mercury telluride, silver selenide and the like, have low absolute fluorescent quantum yield, contain toxic heavy metal elements partially, and have difficult two-way fluorescence intensity and toxicity. Therefore, there is an urgent need to develop a novel fluorescent quantum dot probe with continuously tunable single emission, high fluorescence quantum efficiency and high biocompatibility in the NIR-II full window (900-1700 nm).
Disclosure of Invention
The invention mainly aims to provide a near-infrared silver-gold-selenium fluorescent quantum dot with high quantum efficiency and a preparation method thereof, thereby overcoming the defects in the prior art.
The invention further aims at providing application of the near infrared silver gold selenium fluorescent quantum dot.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a near infrared silver gold selenium fluorescent quantum dot, which comprises the following steps:
carrying out solvothermal reaction on a first uniform mixed reaction system containing a silver source, a selenium source and a weak polar solvent to obtain a silver selenide quantum dot precursor;
and (3) carrying out cation exchange reaction on a second uniform mixed reaction system containing a silver selenide quantum dot precursor and a gold source at 0-200 ℃ for 10-72 h to obtain the near infrared silver gold selenium fluorescent quantum dot.
In some embodiments, the method of making comprises: and carrying out solvothermal reaction on the first uniform mixed reaction system at 100-300 ℃ for 0.5-24 h to obtain the silver selenide quantum dot precursor.
The embodiment of the invention also provides the near infrared silver-gold-selenium fluorescent quantum dot prepared by the method.
Further, the diameter of the near infrared silver gold selenium fluorescent quantum dot is 2-20 nm, and the size distribution is uniform.
Further, the fluorescence emission peak wavelength of the near infrared silver-gold-selenium fluorescence quantum dot is between 800 and 1350nm.
Further, the absolute fluorescence quantum yield of the near infrared silver gold selenium fluorescence quantum dots is more than 90%.
The embodiment of the invention also provides application of any of the near-infrared silver-gold-selenium fluorescent quantum dots in the fields of biological imaging, biomedicine or near-infrared devices (such as near-infrared light emitting diodes) and the like.
Compared with the prior art, the invention has the beneficial effects that:
1) The silver gold selenium quantum dot is obtained by a simple high-temperature solvothermal method, and then by a cation exchange method, the synthesis process is simple in steps, the experimental conditions are controllable, the used reagent is simple and easy to obtain, and the yield of the final product is high, so that the method is suitable for mass production;
2) The final product prepared by the invention is near-infrared silver-gold-selenium fluorescent quantum dots, the size distribution is uniform, the fluorescence emission is in the near-infrared, the emission peak wavelength is in the range of 800-1350 nm, the final product has ultrahigh absolute quantum efficiency (more than 90%) and excellent light stability, does not contain any toxic heavy metal elements, and has wide application prospect in the fields of biological imaging, near-infrared devices and the like;
3) The preparation process of the invention can be further expanded to the preparation process of other near infrared silver gold selenium fluorescent quantum dots, and has higher yield and easy amplification of reaction scale.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the following brief description will be given of the drawings used in the embodiments or the description of the prior art, it being obvious that the drawings described below are only examples of the invention herein, and that other drawings can be obtained from these drawings without the inventive effort of a person skilled in the art.
FIGS. 1 a-1 b are transmission electron micrographs and high resolution transmission electron micrographs of the near infrared silver gold selenium fluorescent quantum dots of example 1 of the present invention, respectively;
FIG. 2 is a powder X-ray diffraction pattern of near infrared silver gold selenium fluorescent quantum dots in example 1 of the present invention;
FIG. 3 is an energy dispersive X-ray spectrum of the near infrared silver gold selenium fluorescent quantum dots of example 1 of the present invention;
fig. 4 a-4 b are fluorescence emission spectra and quantum efficiency measurement spectra of near infrared silver gold selenium fluorescent quantum dots in example 1 of the present invention.
Detailed Description
As described above, in view of the shortcomings of the prior art, the present inventors have long studied and a great deal of practice to find that: the alloy product silver gold selenium quantum dot of the gold element and the silver selenide quantum dot has good near infrared optical property, the absolute quantum efficiency is up to more than 90%, and meanwhile, the alloy product silver gold selenium quantum dot does not contain any toxic heavy metal element. The technical scheme of the invention will be explained in more detail as follows.
As one aspect of the technical scheme of the invention, the preparation method of the near infrared silver gold selenium fluorescent quantum dot comprises the following steps:
carrying out solvothermal reaction on a first uniform mixed reaction system containing a silver source, a selenium source and a weak polar solvent to obtain a silver selenide quantum dot precursor;
and (3) carrying out cation exchange reaction on a second uniform mixed reaction system containing a silver selenide quantum dot precursor and a gold source at 0-200 ℃ for 10-72 h to obtain the near infrared silver gold selenium fluorescent quantum dot.
In some embodiments, the method of making consists essentially of: uniformly mixing a silver source and a selenium source in a weak polar solvent, and performing solvothermal reaction to obtain silver selenide quantum dots; mixing the silver selenide quantum dots with a gold source, and carrying out cation exchange reaction at room temperature to obtain the near-infrared silver-gold-selenium quantum dots with high quantum efficiency, wherein the fluorescence emission peak wavelength is between 800 and 1350nm.
In some preferred embodiments, the preparation method of the high quantum efficiency near-infrared silver-gold-selenium fluorescent quantum dot may specifically include:
uniformly mixing a silver source with a weak polar solvent, and adding a selenium source to perform solvothermal reaction to prepare a silver selenide quantum dot precursor;
and mixing the silver selenide precursor with a gold source at 0-200 ℃ for reaction to obtain the silver-gold-selenium fluorescent quantum dot, wherein the fluorescence emission peak wavelength is 800-1350 nm, and the absolute fluorescence quantum yield is more than 90%.
In some embodiments, the method of making comprises: and uniformly mixing a silver source with a weak polar solvent, and then adding a selenium source to form the first uniform mixing reaction system.
In some embodiments, the preparation method specifically comprises: and carrying out solvothermal reaction on the first uniform mixed reaction system at 100-300 ℃ for 0.5-24 h to obtain the silver selenide quantum dot precursor.
In some embodiments, the mass ratio of the silver source to the selenium source is 1-10:1-10. That is, the preparation method includes: the silver source and the selenium source are taken to be dissolved in the weak polar solvent according to the mass ratio of 1-10:1-10.
The preparation process of the silver selenide precursor provided by the invention is solvothermal reaction, the steps are simple, the experimental conditions are controllable, the used reagent is simple and easy to obtain, and the yield of the final product is higher, so that the silver selenide precursor is suitable for large-scale production.
In some embodiments, the method of making comprises: and uniformly mixing the silver selenide quantum dot precursor, the gold source and the weak polar solvent to form the second uniform mixing reaction system.
In some embodiments, the mass ratio of the silver selenide quantum dot precursor to the gold source is 1-10:1-10. That is, the preparation method includes: and dissolving the silver selenide quantum dot precursor and the gold source in a weak polar solvent according to the mass ratio of 1-10:1-10.
In some embodiments, the silver salt includes any one or a combination of two or more of silver chloride, silver bromide, silver iodide, silver sulfate, silver nitrate, silver carbonate, silver sulfide, silver trifluoroacetate, silver diethyldithiocarbamate, and the like, but is not limited thereto.
In some embodiments, the selenium source includes any one or a combination of two or more of selenium dioxide, selenium powder, sodium selenate, sodium selenite, sodium selenide, diphenyl diselenide, and the like, but is not limited thereto.
In some embodiments, the weak polar solvent includes any one or a combination of two or more of oleylamine, oleic acid, octadecene, octadecylamine, dodecyl amine, dodecyl mercaptan, octyl mercaptan, and octadecyl mercaptan, but is not limited thereto.
In some embodiments, the gold source includes any one or a combination of two or more of sodium chloroaurate, chloroauric acid, gold nitrate, gold chloride, gold hydroxide, gold oxide, gold nanorods, gold particles, and the like, but is not limited thereto.
The foregoing silver salts, selenium sources, less polar solvents, gold sources, and the like may be selected from, but are not limited to, the types listed above.
Further, in an exemplary embodiment, the preparation method may include: firstly, silver nitrate is dissolved in oleylamine, a selenium source is added for reaction for 1-6 hours at 100-300 ℃, and then the silver nitrate is cleaned to obtain a target product silver selenide quantum dot precursor.
Further, the mass ratio of the silver salt to the selenium source is 0.1-1 g to 0.1-1 g.
In some preferred embodiments, the method of making may comprise: and dissolving 0.1-1 g of silver salt in a weak polar solvent.
Further, the preparation method specifically comprises the following steps: and mixing the silver selenide precursor with a gold source, and reacting at 100-200 ℃ to obtain the near infrared silver-gold-selenium fluorescent quantum dot.
Further, the preparation method further comprises the following steps: and after the reaction is completed, cleaning the obtained silver gold selenium fluorescent quantum dots.
Wherein, as one of more specific embodiments, the preparation method may comprise the steps of:
I. mixing silver salt with a weak polar solvent, and uniformly dispersing by ultrasonic waves;
II. Adding a selenium source into the mixed solution finally obtained in the step I, uniformly mixing and dispersing, and reacting at 100-300 ℃ for 0.5-24 h:
III, separating a product obtained by the solvothermal reaction in the step II, and cleaning and drying;
and IV, reacting the product obtained in the step III with a gold source at 0-200 ℃ for 10-72 h to obtain the near infrared silver-gold-selenium fluorescent quantum dot.
The near infrared silver gold selenium fluorescent quantum dot of the final product prepared by the invention has uniform size distribution, the fluorescence emission peak wavelength is between 800 and 1350nm, preferably between 800 and 1200nm, and the final product has ultrahigh absolute fluorescence quantum efficiency (more than 90 percent) and does not contain any toxic heavy metal elements. And the yield of the final product is high, and the preparation process is easy to enlarge the reaction scale.
Furthermore, the preparation process of the invention can be further expanded to the preparation process of other near infrared silver-gold-selenium fluorescent quantum dots, and has higher yield and easy amplification of reaction scale.
As another aspect of the technical scheme of the invention, the invention also relates to the near infrared silver gold selenium fluorescent quantum dot prepared by the method.
Further, the diameter of the near infrared silver gold selenium fluorescent quantum dot is 2-20 nm.
Further, the fluorescence emission peak wavelength of the near infrared silver-gold-selenium fluorescence quantum dot is between 800 and 1350nm, preferably between 800 and 1200nm, the absolute fluorescence quantum yield is more than 90%, and the near infrared silver-gold-selenium fluorescence quantum dot does not contain any toxic heavy metal elements.
As another aspect of the technical scheme of the invention, the invention also provides the near infrared silver gold selenium fluorescent quantum dot which has uniform shape and size, high absolute quantum yield and no toxic heavy metal element, and has important application prospect in the fields of biological imaging, biomedicine or near infrared devices and the like.
Another aspect of the embodiments of the present invention further provides an application of any one of the aforementioned near-infrared silver-gold-selenium fluorescent quantum dots in the fields of bioimaging, biomedical or near-infrared devices, etc.
Further, the near infrared device may be a near infrared light emitting diode, but is not limited thereto.
In summary, by adopting the technical scheme, the silver selenide quantum dots are prepared by a simple high-temperature solvothermal method, and then the silver gold selenide quantum dots are obtained by a cation exchange method, so that the synthesis process is simple and controllable, the yield is high, the large-scale preparation can be realized, the obtained product is uniform in size, fluorescence emission is in the near infrared, the fluorescence emission has high quantum efficiency and excellent light stability, and the fluorescence quantum dots have wide application prospects in the fields of biological imaging, near infrared devices and the like.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below with reference to several preferred embodiments, but the present invention is not limited to the following embodiments, and the technical solutions and modifications may be made by those skilled in the art under the core guiding ideas of the present invention without essential modifications and remain within the scope of the present invention. Unless otherwise indicated, the various reagents used in the following examples are well known to those skilled in the art and may be obtained by commercial means or the like. The experimental methods in the following examples, in which specific conditions are not specified, are generally conducted under conventional conditions or under conditions recommended by the manufacturer.
Example 1
Dissolving 0.06g of silver nitrate in 20mL of oleylamine, uniformly dispersing by ultrasonic, then adding 0.06 selenium powder, reacting for 5 hours at 200 ℃ to obtain silver selenide quantum dot precursor (0.6 g), then adding 0.06g of chloroauric acid, and reacting for 48 hours at 100 ℃ to obtain the near infrared silver-gold-selenium fluorescent quantum dot.
As can be seen from fig. 1a to fig. 1b, the near-infrared silver-gold-selenium fluorescent quantum dot product obtained in this example has a uniform morphology and a uniform size, and the size is about 4.8nm, wherein fig. 1a is a transmission electron micrograph of the near-infrared silver-gold-selenium fluorescent quantum dot, and fig. 1b is a high-resolution transmission electron micrograph. Referring to fig. 2 and 3, the nanoparticle material is a silver-gold-selenium compound as can be seen by powder X-ray diffraction and energy dispersive X-ray spectroscopy.
Dispersing the silver gold selenium quantum dots in chloroform. The luminescence spectrum and absolute fluorescence quantum yield were measured using a near infrared fluorescence spectrometer. As can be seen from fig. 4a and 4b, the silver-gold-selenium fluorescence quantum dot is located at 800-1200 nm, and the absolute quantum efficiency is 90.3%.
Example 2
Dissolving 0.06g of silver carbonate in 20mL of octanethiol, uniformly dispersing by ultrasonic, adding 0.8g of selenium dioxide, reacting for 2 hours at 250 ℃ to obtain a silver selenide quantum dot precursor (0.05 g), and adding 0.5g of gold nitrate, reacting for 10 hours at 200 ℃ to obtain the near infrared silver gold selenium fluorescent quantum dot.
Example 3
Dissolving 0.6g of silver bromide in 20mL of oleic acid, uniformly dispersing by ultrasonic, adding 0.6 sodium selenate, reacting for 1h at 200 ℃ to obtain silver selenide quantum dot precursor (0.1 g), adding 0.1g of sodium chloroaurate, and reacting for 48h at 100 ℃ to obtain the near infrared silver-gold-selenium fluorescent quantum dot.
Example 4
Dissolving 0.06g of silver chloride in 20mL of dodecyl mercaptan, uniformly dispersing by ultrasonic, then adding 0.06g of sodium selenide, reacting for 5 hours at 100 ℃ to obtain a silver selenide quantum dot precursor (0.06 g), then adding 0.06g of gold chloride, and reacting for 72 hours at 0 ℃ to obtain the near infrared silver-gold-selenium fluorescent quantum dot.
Example 5
Adding 0.06g of silver iodide into 20g of octadecylamine, uniformly dispersing by ultrasonic, then adding 0.06 diphenyl diselenide, reacting for 24 hours at 200 ℃ to obtain silver selenide quantum dot precursor (0.03 g), then adding 0.05g of gold hydroxide, and reacting for 72 hours at 0 ℃ to obtain the near infrared silver-gold-selenium fluorescent quantum dot.
Example 6
Dissolving 0.06g of silver diethyl dithiocarbamate in 20mL of octadecanethiol, uniformly dispersing by ultrasonic, then adding 0.06 selenium powder, reacting for 0.5h at 300 ℃ to obtain silver selenide quantum dot precursor (0.06 g), then adding 0.06g of gold oxide, and reacting for 72h at 0 ℃ to obtain the near infrared silver-gold-selenium fluorescent quantum dot.
Example 7
Dissolving 0.06g of silver trifluoroacetate in 20mL of octadecene, uniformly dispersing by ultrasonic, then adding 0.06 selenium powder, reacting for 24 hours at 200 ℃ to obtain silver selenide quantum dot precursor (0.06 g), then adding 0.06g of gold nanorod, and reacting for 72 hours at 0 ℃ to obtain the near infrared silver gold selenium fluorescent quantum dot.
In addition, the inventor also uses other raw materials listed above and other process conditions to replace various raw materials and corresponding process conditions in the embodiment l-7 to carry out corresponding tests, and the appearance, performance and the like of the obtained near-infrared silver-gold-selenium fluorescent quantum dot are ideal and are basically similar to those of the embodiment l-7.
The silver gold selenium quantum dot is obtained through a simple high-temperature solvothermal method, and then through a cation exchange method, the synthesis process is simple and controllable, the yield is high, the large-scale preparation can be realized, meanwhile, the obtained product is uniform in size, fluorescence emission is in near infrared, the quantum dot has high quantum efficiency and excellent light stability, and the silver gold selenium quantum dot has wide application prospects in the fields of biological imaging, near infrared devices and the like.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the present invention.
Throughout this disclosure, where a composition is described as having, comprising, or including a particular component, or where a process is described as having, comprising, or including a particular process step, it is contemplated that the composition of the teachings of the present invention also consist essentially of, or consist of, the recited component, and that the process of the teachings of the present invention also consist essentially of, or consist of, the recited process step.
Unless specifically stated otherwise, the use of the terms "comprising (include, includes, including)", "having (has, has or has)" should generally be understood to be open-ended and not limiting.
It should be understood that the order of steps or order in which a particular action is performed is not critical, as long as the present teachings remain operable. Furthermore, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (9)
1. The preparation method of the near infrared silver gold selenium fluorescent quantum dot is characterized by comprising the following steps of:
carrying out solvothermal reaction on a first uniform mixed reaction system containing a silver source, a selenium source and a weak polar solvent for 0.5-24 hours at the temperature of 100-300 ℃ to obtain a silver selenide quantum dot precursor, wherein the mass ratio of the silver source to the selenium source is 1-10: 1-10, wherein the weak polar solvent is selected from any one or more than two of oleylamine, oleic acid, octadecene, octadecylamine, dodecyl amine, octyl mercaptan and octadecyl mercaptan;
carrying out cation exchange reaction on a second uniform mixed reaction system containing a silver selenide quantum dot precursor and a gold source at 0-200 ℃ for 10-72 h to obtain a near infrared silver-gold-selenium fluorescent quantum dot, wherein the mass ratio of the silver selenide quantum dot precursor to the gold source is 1-10: 1-10, wherein the gold source is selected from any one or more than two of sodium chloroaurate, chloroauric acid, gold nitrate, gold chloride, gold hydroxide, gold oxide, gold nanorods and gold particles;
the diameter of the near infrared silver-gold-selenium fluorescent quantum dot is 2-20 nm, the size distribution is uniform, the fluorescence emission peak wavelength is 800-1350 nm, and the absolute fluorescence quantum yield is more than 90%.
2. The preparation method according to claim 1, characterized by comprising: and uniformly mixing a silver source with a weak polar solvent, and then adding a selenium source to form the first uniform mixing reaction system.
3. The production method according to claim 1 or 2, characterized by comprising: and carrying out solvothermal reaction on the first uniform mixed reaction system at 100-300 ℃ for 1-6 hours to obtain the silver selenide quantum dot precursor.
4. The preparation method according to claim 1, characterized by comprising: and uniformly mixing the silver selenide quantum dot precursor, the gold source and the weak polar solvent to form the second uniform mixing reaction system.
5. The method of manufacturing according to claim 1, characterized in that: the silver salt is selected from any one or more than two of silver chloride, silver bromide, silver iodide, silver sulfate, silver nitrate, silver carbonate, silver sulfide, silver trifluoroacetate and silver diethyl dithiocarbamate.
6. The method of manufacturing according to claim 1, characterized in that: the selenium source is selected from one or more than two of selenium dioxide, selenium powder, sodium selenate, sodium selenite, sodium selenide and diphenyl diselenide.
7. The method of manufacturing according to claim 1, characterized in that: the fluorescence emission peak wavelength of the near infrared silver-gold-selenium fluorescence quantum dot is 800-1200 nm.
8. Use of the near infrared silver gold selenium fluorescent quantum dots prepared by the preparation method of any one of claims 1-7 in the field of bioimaging or near infrared devices.
9. The use according to claim 8, characterized in that: the near infrared device is a near infrared light emitting diode.
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| JP2022536547A JP7378857B2 (en) | 2021-01-20 | 2021-12-21 | Preparation method of near-infrared silver gold selenium fluorescent quantum dots |
| EP21920841.0A EP4092095A4 (en) | 2021-01-20 | 2021-12-21 | Fluorescent quantum dots and preparation method therefor and use thereof |
| PCT/CN2021/140056 WO2022156467A1 (en) | 2021-01-20 | 2021-12-21 | Fluorescent quantum dots and preparation method therefor and use thereof |
| US17/785,420 US20230247846A1 (en) | 2021-01-20 | 2021-12-21 | Fluorescent quantum dots as well as preparation method and use thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104007095A (en) * | 2014-05-30 | 2014-08-27 | 桂林理工大学 | Method for measuring concentration of nanogold by adopting near infrared luminescent quantum dot fluorescent spectrometry |
| CN104513664A (en) * | 2013-09-27 | 2015-04-15 | 深圳先进技术研究院 | Near-infrared silver-indium-selenium quantum dot and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104513664A (en) * | 2013-09-27 | 2015-04-15 | 深圳先进技术研究院 | Near-infrared silver-indium-selenium quantum dot and preparation method thereof |
| CN104007095A (en) * | 2014-05-30 | 2014-08-27 | 桂林理工大学 | Method for measuring concentration of nanogold by adopting near infrared luminescent quantum dot fluorescent spectrometry |
Non-Patent Citations (2)
| Title |
|---|
| General Synthetic Approach to Heterostructured Nanocrystals Basedon Noble Metals and I−VI, II−VI, and I−III−VI Metal Chalcogenides;Liu Minghui;《Langmuir》;20140729;第30卷;全文 * |
| Synthesis and Thermoelectric Properties of Noble Metal Ternary Chalcogenide Systems of Ag−Au−Se in the Forms of Alloyed Nanoparticles and Colloidal Nanoheterostructures;Mariona Dalmases;《Chemistry of Materials》;20160909;第28卷;第7018页"Experimental Section"，第7026页右栏第1段，图2，图1(c) * |
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